Preparing water insoluble anthraquinone dyestuffs

ABSTRACT

WHEREIN R1 is a saturated or unsaturated alkyl, cycloalkyl, aryloxyalkyl, aralkyl, aralkoxyalkyl or hydroxyalkyl having two to 12 carbon atoms, which comprises reacting 1-hydroxy-3-imino4,7-diamino-5,6-phthalylisoindolenine or its tautomer with an alkylating agent in water or in an aqueous medium containing a small amount of an organic solvent.   Improvement for preparing water insoluble anthraquinone dyestuffs represented by the formula,

I United States Patent 51 3,668,2 1 9 Otsuka et al. 1 June 6, 1972 [54] PREPARING WATER INSOLUBLE ANTHRAQUINONE DYESTUFFS Primary Examiner-Alex Mal-e1 Assistant Examiner-Joseph A. Narcavage [72] Inventors: Toklo Otsuka, Ashlya; Shozo Sasabe, Atmmey StevenS, Davis Miner & Masher Ibaragi; Hiroyuki Nakagawa, Nishinomiya, all of Japan 57] ABSTRACT [73] As ign Sllmilomo Chemical p y, Improvement for preparing water insoluble anthraquinone Osaka, Japan dyestufis represented by the formula, [22] Filed: Apr. .1, 1970 o NH: 0 [21] App]. No.: 24,828 g3 NR1 [30] Foreign Application Priority Data C J ..44 27500 1 6 Apr 9, 1969 apan NH: H

V 52 US. Cl ..260/325 i511 1m. CI. wherein 1 is a saturated or n aturated alkyl, cycloalkyl, 581 Field of Search ..260/325 arylmyalkyl aralkyl amnwxyalky' hydmxyalky] having two to 12 carbon atoms, which comprises reacting l-hydroxy- [56] References Cited 3-imino-4,7-diamino-5,G-phthalylisoindolenine or its tautomer with an alkylating agent in water or in an aqueous medi- UNITED STATES PATENTS um containing a small amount of an organic solvent.

Akamatsu et al ..260/325 7 Claims, No Drawings PREPARING WATER INSOLUBLE ANTHRAQUINONE DYESTUFFS The present invention relates to improvements in the preparation of water insoluble blue disperse dyestuffs of anthraquinone series represented by the formula,

with an unsubstituted'or substituted alkylating agent in water or in an aqueous medium containing a small amount of an organic solvent.

The above-mentioned compounds represented by the formulas (ll) and (III) are tautomers to each other and are to be considered essentially a single compound.

For convenience, the compounds are hereinafter referred to isoindolenine.

So far, the reaction betweenthe isoindolenine and an alkylating agent such as alkyl p-toluenesulfonates is conducted in an organic aprotic or weak basic solvent as described in, for example, Japanese Patent Publication No. 3712/1966 US. Pat. No.'3,326,934). Q

It is considered inevitable to conduct the reaction between the isoindolenine and the alkylating agent in non-aqueous state because the presence of water brings about the decomposition of the alkylating agent. I

And therefore, the reaction is always conducted with use of expensive organic solvents and with complicated operations such as drying and pulverizing the isoindolenine and dehydrating the alkylating agent.

Surprising is finding that the reaction between the isoindolenine and the alkylating agent may be conducted in water or in the aqueous medium with high yield and good qualities of the water insoluble anthraquinone dyestuffs represented by the formula (I).

It is therefore the principal object of the present invention to avoid the difficulties heretofore encountered in the alkylation in organic solvents for the production of the water insoluble anthraquinone dyestuffs (l It is a further object to provide a process for producing water insoluble anthraquinone dyestuffs (I) which is not only simple but also inexpensive in operation.

Another object of the present invention is to provide an improved process for the production of the water insoluble anthraquinone dyestuffs (l).

Another object of the invention is the provision of a process of alkylation in water or an aqueous solvent in a commercially feasible manner.

These and other objects of the present invention can be accomplished by the provision of, in the process for the production of the water insoluble anthraquinone dyestufi's (l) by reacting the isoindolenine with alkylating agents in organic solvents, the improvement which comprises conducting the reaction in water or in an aqueous medium containing a small amount of an organic solvent.

Thus, the process of the present invention can be practiced commercially at a low cost and is simple in operation because it requires no use of an expensive organic solvent. The greatest advantage of the process of the present invention is the fact that the isoindolenine and an alkylating agent as starting materials can be directly used in the form of wet cake without drying or pulverizing them and there is no necessity for completely dehydrating the starting materials before use. It is of high value in the practical commercial manufacture of the water insoluble anthraquinone dyestufis (I).

More concretely, in the process of the present invention, the isoindolenine may be reacted with an unsubstituted or substituted alkylating agent in water or man aqueous medium containing a small amount of an organic solvent in the presence of an acid binding agent at a temperature of 60 to 150 C.

The unsubstituted or substituted alkylating agents which may be used in the present invention are represented by the formula,

R, S0 O R or the formula,

R, X v wherein R is as defined above; R represents an aromatic or aliphatic radical; and X represents a halogen atom. They include, for example, methoxyethyl p-toluenesulfonate, ethoxyethyl p-toluenesulfonate, butoxyethyl p-toluenesulfonate, ethyl p-toluenesulfonate, propyl p-toluenesulfonate, cyclohexyl benzenesulfonate, phenylethyl p-toluenesulfonate, butylcellosolve p-toluenesulfonate and halides of the alkyls or substituted alkyls such as allyl chloride, B-methallyl chloride and benzyl chloride. The halogens are advantageously chlorine and bromine.

.. the present process.

It is, however, preferable to use the solvents in an amount of 30 percent by weight or less based on the weight of water only from economical point of view.

The acid binding agents include organic weakly basic compounds such as tertiary amines i.e. pyridine, picolines, dimethylaniline and diethylaniline and mixtures thereof, and sodium and potassium bicarbonates as well as sodium, potassium, magnesium and calcium carbonates.

The water insoluble anthraquinone dyestuffs of the formula (I) produced by the process of the present invention have high afi'mity for synthetic fibers, particularly polyester fiber and can give greenish blue dyeings with fastness to light, sublimation and washing.

. The following examples will serve to illustrate the practice of the invention in more detail, but are, of course, not intended to limit the scope of the present invention.

Example 1 A mixture of g. of wet cake containing 16 g. of l-hydroxy-3-imino-4,7-diamino-5,-phthaloylisoindolenine, 80 cc. of water, 4 g. of monochlorobenzene, 1 l g. of sodium carbonate, 0.1 g. of pyridine and 28.5 g. of isopropyl p-toluenesulfonate was heated at C. for 20 hours and then cooled. The crystals separated by filtration were washed with methanol and water and dried to obtain 15.5 g. of a greenish blue dyestuff for polyester fiber represented by the structural formula,

O NH2 Example 2 A mixture of 96 g. of wet cake containing 12 g. of l-hydroxy-3-imino-4,7-diamino-5,-phthaloylisoindolenine, 40 c.c. of water, 8.4 g. of sodium bicarbonate, l g. of pyridine and 21.4 g. of n-butyl p-toluenesulfonate was heated in an autoclave at 110 to 120 C. for 7 hours and then cooled. The crystals separated by filtration were thoroughly washed with methanol and then with water to obtain 1 1.85 g. of a dyestuff represented by the structural formula,

0 NHz f I 1 When the pyridine was replaced by dimethylaniline in this example, a similar result was obtained. Example 3 A mixture of 122 g. of wet cake containing 14 g. of 1- hydroxy-3-imino-4,7-diamino-5,6- hthaloylisoindolenine, 12 g. of sodium carbonate, 1.5 g. of pyridine and 28 g. of B- methoxyethyl p-toluenesulfonate was heated at 95 to 100 C. for 20 hours and then cooled. The crystals separated by filtration were washed with methanol and water and dried to obtain 14.1 g. of a greenish blue dyestuff for polyester fiber represented by the structural formula,

0 NHa i I /N CHgCHzOCH 1 C 0 NHz LE Example 4 When the B-methoxyethyl p-toluencsulfonate was replaced by phenylethyl p-toluenesulfonate in Example 3, 15.1 g. of a dyestuff represented by the structural formula,

NH: LB

was obtained. Example 5 A mixture of 30 g. of wet cake containing 3 g. of l-hydroxy- 3-imino-4,7-diamino-5,6-phthaloylisoindolenine, 5 g. of nitrobenzene, 5 g. of sodium bicarbonate, 2 g. of picoline and 3.7 g. of benzyl chloride was heated at 100 C. for hours. The reaction mixture was then cooled and diluted with methanol. The crystals separated by filtration were washed with methanol and water and dried to obtain 3.2 g. of a dyestuff represented by the structural formula,

NH: O

NHz LB Example 6 A mixture of 100 g. of wet cake containing 10 g. of lhydroxy-3-imino-4,7-diamino-5,G-phthaloylisoindolenine, 10 g. of isobutanol, 8 g. of sodium carbonate, 0.5 g. of pyridine and 16 g. of n-butyl ptoluenesulfonate was heated at 95 to 1 100 C. for 20 hours and then cooled. The crystals separated by filtration were thoroughly washed with methanol and then with water to obtain 10.1 g. of a dyestuff represented by the structural formula,

20 0 NHz l H-CHzCHzCHzCH Example 7 A mixture of g. of wet cake containing 15 g. of l-hydroxy-3-imino-4,7-diamino-5,G-phthaloylisoindolenine, 12 g. of sodium carbonate, 1.5 g. of pyridine, 3.7 g. of nitrobenzene and 30 g. of butylcellosolve p-toluenesulfonate was heated at 90 to 95 C. for 15 hours and then cooled. The crystals separated by filtration were thoroughly washed with methanol and then with water to obtain 17.6 g. of a dyestuff represented by the formula,

wherein R. represents a saturated or unsaturated alkyl, alkoxyalkyl, cycloalkyl, aryloxyalkyl, aralkyl, aralkyloxyalkyl or hydroxyalkyl having two to 12 carbon atoms, by reacting a compound represented by the formula,

O I NHZ g C A 1 111: LB

or its tautomer represented by the formula,

I if NHz NH with unsubstituted or substituted alkylating agent in an organic solvent, the improvement which comprises conducting the reaction in water or in an aqueous medium containing 30 wherein is as defined in claim I; R, is an aromatic or aliphatic radical; and X is a halogen atom.

3. A process according to claim 2 wherein said alkylating agent is selected from the group consisting of methoxyethyl ptoluenesulfonate, ethoxyethyl p-toluenesulfonate, butoxyethyl p-toluenesulfonate, ethyl p-toluenesulfonate, propyl ptoluenesulfonate, cyclohexyl benzenesulfonate, phenylethyl ptoluenesulfonate, butylcellosolve p-toluenesulfonate, allyl chloride, B-methallyl chloride and benzyl chloride.

4. A process according to claim 3 wherein said halides are chlorides or bromides.

5. A process according to claim 1, wherein the reaction is conducted in the presence of an acid binding agent.

6. A process according to claim 5, wherein the acid binding agent is sodium and potassium bicarbonates, sodium, potassium, magnesium and calcium carbonates, pyridine, picoline,

dimethylaniline, diethylaniline or a mixture thereof.

7. A process according to claim 1, wherein the reaction is conducted at a temperature from 60 to C. 

2. A process according to claim 1 wherein said alkylating agent is a compound represented by the formula, R2 - SO2 - O - R1 or R1 - X wherein 1 is as defined in claim 1; R2 is an aromatic or aliphatic radicaL; and X is a halogen atom.
 3. A process according to claim 2 wherein said alkylating agent is selected from the group consisting of methoxyethyl p-toluenesulfonate, ethoxyethyl p-toluenesulfonate, butoxyethyl p-toluenesulfonate, ethyl p-toluenesulfonate, propyl p-toluenesulfonate, cyclohexyl benzenesulfonate, phenylethyl p-toluenesulfonate, butylcellosolve p-toluenesulfonate, allyl chloride, Beta -methallyl chloride and benzyl chloride.
 4. A process according to claim 3 wherein said halides are chlorides or bromides.
 5. A process according to claim 1, wherein the reaction is conducted in the presence of an acid binding agent.
 6. A process according to claim 5, wherein the acid binding agent is sodium and potassium bicarbonates, sodium, potassium, magnesium and calcium carbonates, pyridine, picoline, dimethylaniline, diethylaniline or a mixture thereof.
 7. A process according to claim 1, wherein the reaction is conducted at a temperature from 60* to 150* C. 